Emulsified water blended fuels produced by using a low energy process and novel surfuctant

ABSTRACT

A novel low energy process to produce water in oil emulsions in particular water blended fuels by employing a low molecular weight surfactant with an emulsifier package.

FIELD OF INVENTION

[0001] The invention relates to a novel low energy process to produce awater in oil emulsion, in particular water blended fuels with goodemulsion stability. More particularly, the invention relates to the useof a low molecular weight surfactant to make a water in oil emulsion bya low energy, low shear process.

BACKGROUND OF THE INVENTION

[0002] Internal combustion engines, especially diesel engines, usingwater fuel blends results in the combustion chamber producing lowernitrogen oxides (NO_(x)), hydrocarbons and particulate matter emissions.NO_(x) emissions have become an important environmental issue because itcontributes to smog and air pollution. Governmental regulations andenvironmental concerns have driven the need to reduce NO_(x) emissionsfrom engines. In particular, the U.S. Clean Air Act will require about90% to 95% reduction of the current level of internal combustion enginesemissions by the year 2007. Similar regulations are expected in Europeand other parts of the industrialized world.

[0003] Diesel fueled engines produce NO_(x) due to the relatively highflame temperatures reached during combustion. The reduction of NO_(x)production conventionally includes the use of catalytic converters,using “clean” fuels, recirculation of exhaust and engine timing changes.These methods are typically expensive or complicated to be readilycommercially available. Water is inert toward combustion, but lowers thepeak combustion temperature resulting in reduced particulates and NO_(x)formation. When water is added to the fuel it forms an emulsion andthese emulsions are generally unstable. Stable water in fuel emulsionsof a small particle size are difficult to reach and maintain.

[0004] The use of emulsified fuels to reduce emissions have beendisclosed in other patents and patent applications of Applicant, such asU.S. Pat. Nos. 6,280,485, 6,383,237, 6,368,367, 6,368,366 and 6,280,485and U.S. Ser. No. 09/761,482 all incorporated herein by reference andassigned to the assignee of the present application. Emulsified fuelshave been made by high energy intensive processes. It would beadvantageous to develop a low energy process to make stable water infuel emulsions.

[0005] The present invention has discovered the use of certain lowmolecular weight surfactants that lower interfacial tension at the wateroil interface resulting in a low energy process to make a water in oilemulsion fuels.

[0006] The term “NO_(x)” is used herein to refer to any of the nitrogenoxides, NO, NO₂, N₂O, or mixtures of two or more thereof. The terms“water-in-oil” emulsion, “water emulsion”, “emulsions”, “water blendedfuel”, “emulsified water fuel” and other variations are interchangeable.

SUMMARY OF THE INVENTION

[0007] The invention relates to an emulsified water in oil compositioncomprising:

[0008] A. a fuel in the range of about 50% to about 99% by weight of thecomposition;

[0009] B. a water in the range of about 1% to about 50% by weight of thecomposition;

[0010] C. an emulsifier in the range of about 1% to about 50% by weightof the composition;

[0011] D. a low molecular weight surfactant in the range of about 0.001%to about 15% by weight of the composition wherein the surfactantcomprises:

[0012] i) natural fats;

[0013] ii) non-ionic and ionic surfactants;

[0014] iii) co-surfactants;

[0015] iv) fatty acids and their amine salts; or

[0016] v) combinations thereof; and

[0017] E. optionally ammonium nitrate.

[0018] The surfactant lowers the interfacial tension of the water in oilinterface during emulsion and formation and is a low molecular weightsurfactant that is less than or equal to 950 g/mol.

[0019] Further, the invention relates to a low energy process for makinga water in oil emulsion comprising emulsifying a fuel, a water, anemulsifier, and a low molecular weight surfactant. The water in oilemulsion is produced utilizing a low energy processing technology usinglow shear rates and does not need to employ high shear rates.

[0020] The invention further relates to a low energy process to producean emulsified water in oil composition from a concentrate comprisingemulsifying a portion of a fuel, a portion to substantially all of awater depending on whether it is an emulsified concentrate or anadditive concentrate, substantially all of an emulsifier, substantiallyall of a low molecular weight surfactant to form a concentrate emulsion;and then diluting the concentrated emulsion with the remaining portionof fuel and water at the time of use.

[0021] The water in oil emulsion provides good emulsion stability. Thewater in oil composition is useful as a fuel for stationary and/orcombustion engines and/or open flame burning apparatus.

DETAILED DESCRIPTION

[0022] The invention discloses a stable emulsified water in oilcomposition made by a low energy process by low shearing the emulsion.The emulsified water in oil composition employs a low molecular weightsurfactant so that a low shear rate mixing condition can be used to makethe emulsion.

[0023] Surfactant

[0024] The surfactant is a small surfactant, having a molecular weight(Mw) of about less than or equal to about 950 g/mol, in anotherembodiment about 900 g/mol to about 30 g/mol, in another embodimentabout 400 g/mol to about 90 g/mol, and in another embodiment about 350g/mol to about 150 g/mol. Further the low molecular weight surfactanthas properties to lower the interfacial tension at the water/oilinterface during emulsion formation. The low molecular weight surfactantfurther orients itself to the water/oil interface quickly by populatingthe water oil interface. The use of the low molecular weight surfactantresults in a low energy process to make the water in oil emulsion, inparticular an emulsified water fuel.

[0025] The surfactant includes but is not limited to a) natural fats; b)non-ionics surfactants; c) co-surfactants; d) fatty acids and theiramine salts; and e) combinations thereof. The surfactant is in the rangeof about 0.001% to about 15%, in another embodiment about 0.01% to about10%, in another embodiment about 0.05% to about 5%, and in anotherembodiment about 0.1% to about 3% by weight of the water in oilcomposition. The surfactants can be used alone or in combination. In oneembodiment the preferred surfactant is a natural fat surfactant.

[0026] The natural fat surfactants include but are not limited totriglycerides, hydrolyzed triglycerides, oxidized products oftriglycerides, vegetable oils, refined vegetable oils, used vegetableoils and the like. The preferred natural fat surfactant is a refinedused vegetable oil. The natural fats can be used alone or incombination.

[0027] The non ionic and ionic surfactants include but are not limitedto alkyl ethoxylates, ethoxylated alkylphenols, alkyl glucosides,ethoxylated alcohols, ethoxylated amines, amides derived from fattyacids and/or alcohols, ethers or fatty alcohols, esters of fatty acidsand the like. In addition the non-ionic and ionic surfactants have ahydrophilic lipohilic balance (HLB) in the range of about 2 to about 40,in one embodiment, about 2 to about 10, in one embodiment about 10 toabout 15 and in another embodiment about 4 to about 8. Examples of thesenon-ionic and ionic surfactants are disclosed in McCutcheon'sEmulsifiers and Detergents, 1993, North American & InternationalEdition. Some examples include but are not limited to alkanolamides,alkylarylsulfonates, amine oxides, poly(oxyalkylene) compounds,including block copolymers comprising alkylene oxide repeat units (e.g.,Pluronic™ s), carboxylated alcohol ethoxylates, ethoxylated alcohols,ethoxylated alkyl phenols, ethoxylated amines and amides, ethoxylatedfatty acids, ethoxylated fatty esters and oils, fatty esters, glycerolesters, glycol esters, imidazoline derivatives, lecithin andderivatives, lignin and derivatives, monoglycerides, diglycerides andderivatives, phosphate esters and derivatives, propoxylated andethoxylated fatty acids or alcohols or alkyl phenols, sorbitanderivatives, sucrose esters and derivatives, sulfates or alcohols orethoxylated alcohols, sulfonates of dodecyl and tridecyl benzenes orcondensed naphthalenes or petroleum and the like. Preferably the nonionic surfactants are Neodol 25-3, C12-C14 alcohol with two ethoxylatesand Ethomeen C12. The non ionic and ionic surfactants may be used aloneor in combination.

[0028] Additionally, the ethoxylated alcohols include but are notlimited to oleyl alcohol with 5 ethoxylates, Tomadol 91-8 (purchasedfrom Tomah Chemical) and the like. The ethoxylated alcohol containsabout 5 to about 24, preferably about 8 to about 20 and more preferablyabout 5 to about 12 carbon atoms with about 3 to about 30 preferablyabout 5 to about 25 and more preferably about 5 to about 10 ethyleneoxide groups. Preferably the ethoxylated alcohol is oleyl alcohol with 5ethoxylates. The ethoxylated alcohols may be used alone or incombination.

[0029] Another example of non-ionic and ionic surfactants include butare not limited to IGEPAL CO-630, (nonylphenoxypoly(ethyleneoxy)ethanol; nonoxynol-8), IGEPAL CO-430, IGEPAL CO 530, available fromRhone-Poulenc, Cranbury, N.J., USA; TERGITOL® NP-9(a-(4-nonylphenyl)-∞-hydroxypoly(oxy-1,2-ethanediyl), available fromUnion Carbide Corporation, Danbury, Conn., USA); and alcohol ethoxylatesavailable from Tomah Products, Inc. under the name “Tomadol”™ alcoholethoxylates and the like.

[0030] In another embodiment the non-ionic and ionic surfactants includebut are not limited to sorbitan esters of fatty acids, sorbitanmonooleate (SMO); sorbitan monoisostearate (SMIS); glycerol esters likeglycerol monooleate (GMO); glycerol dioleate; and mono-unsaturated acidssuch as oleic and elaidic acid; poly-unsaturated acids such as linoleicand linolenic acid; 1,6-dilauryl diglycerol; monoleyl diglycerol; monocetyl ether of glycerol; mono oleyl glycerol; diethylene glycolmono-stearate; and the like. In one embodiment the preferred non-ionicsurfactants are glycerol monooleate, sorbitan monooleate andcombinations thereof.

[0031] In another embodiment the non-ionic and ionic surfactants includebut are not limited to esters of the fatty acids include but are notlimited to glyceryl mono-oleate, glyceryl monostearate, glycerylmonoricinolaeate, pentaerythritol monolaurate, pentaerythritol mono anddioleate, pentaerythritol monocaprylate, mono, di, and triethyleneglycol mono-oleate, propylene glycol monoricinoleate; monoethyleneglycol mono-oleate, triethylene glycol monostearate, sorbitolmonolaurate, mannitol mono-oleate, mannitol dioleate, sorbitol,dioleate, sorbitan dioleate, sorbitan mono and dilaurate, mannitan monoand distearate, mannitan mono and dioleate, sorbitan mono anddipalmitate, sorbitan sesquioleate, mannitan monolaurate, and the like.

[0032] Partial esters obtained from polyhydric alcohols are useful asthe surfactant include but are not limited to the cyclic ether-alcoholesters which have been modified by being further reaction with analkylene oxide or a polyalkyene oxide. For example, a sorbitanmono-oleate may be further modified by treatment with ethylene oxide toform the hydroxylether or sorbitan mono-oleate. Other modified esters ofthis type may be the polyoxyalklene sorbitan monostearate,polyoxyalkylene sorbitan mono-oleate, polyoxyalkylene sorbitanmonolaurate, polyoxyalkylene sorbiitan di and tri-oleate, oleic ester ofpolyoxyalkylene mannitol, and the like. In another embodiment thenon-ionic surfactants include but are not limited to the etherificationof the cyclic ether-alcohols of fatty acids containing 12 or more carbonatoms and may be derived from natural fats and oils or pure fatty acidsor their mixtures may be used. The free fatty acids may be exemplifiedby capric, palmitic, oleic, stearic acid or the like. In addition to thefatty acids other acids may be used and may be exemplified bynaphthenic, sulfonic, salicylic acids and the like.

[0033] In another embodiment the non-ionic and ionic surfactants includebut are not limited to fatty acid alkanol amides such as available fromWitco Corporation under the name SCHERCOMID™, SCHERCOMIDT™SO-A andOleamide DEA, lauric acid, myristic acid, coconut acid, coconut oil,oleic acid, tall oil fatty acid, linoleic acid, soybean oil, apricotkernel oil, wheat germ oil, monocarboxylic fatty acids, triglycerides,and mixtures thereof.

[0034] The co-surfactant has sufficient polar groups to render theco-surfactant partially soluble in both phases. The co-surfactantsinclude but are no limited to alcohols, amines, amides, esters, ketones,ethers and mixtures thereof. The co-surfactant has at least 1 to about24, in another embodiment about 1 to about 10, in another embodimentabout 1 to about 8 carbon atoms. The co-surfactants may be used alone orin combination.

[0035] The alcohol co-surfactant has about 1 to about 6, in anotherembodiment about 1 to about 4 and in another embodiment 1 to 3 hydroxygroups in the molecule. Such alcohols may be aliphatic, saturated orunsaturated, and straight chain or branched or cyclic derivativesthereof. Saturated, aliphatic, straight chain alcohols are preferred.The alcohol surfactants include but are not limited to propylene glycol,ethylene glycol, isopropanol, 2 ethyl hexanol, stearyl alcohol, oleylalcohol, methanol, ethanol and the like. The preferred alcoholsurfactant is propylene glycol. The alcohols may be used alone or incombinations.

[0036] The fatty acids and their amine salts include but are not limitedto N,N-diethy ethanolamine salts of oleic acid, tall oil fatty acids,stearic acid, palmitic acid, lauric acid and the like. The preferablefatty acid and their amine salt is oleic acid-diethyl ethanol aminesalt. The fatty acids and their amine salts can be used alone or incombination.

[0037] The water in oil emulsion is comprised of a continuousfuel-phase, a discontinuous water or aqueous phase, an emulsifyingamount of emulsifier and a low molecular weight surfactant so that theprocess does not require high speed shear to emulsify the fuel andwater.

[0038] In the practice of the present invention the water in oilemulsion is made by a batch, semi-batch or a continuous process. Aconcentrate may be made and used. The process is capable of monitoringand adjusting the flow rates of the fuel, emulsifier, surfactant,additives and/or water to form a stable emulsion with the desired waterdroplet size. The water phase of the emulsified fuel is comprised ofdroplets having a mean diameter of about 1.0 microns or less, in anotherembodiment about 0.8 microns or less, in another embodiment about 0.5microns or less, in another embodiment about 0.15 microns or more, inanother embodiment about 1.0 micron to about 0.5 microns, and in anotherembodiment about 1.0 micron to about 0.2 microns.

[0039] The emulsified fuel may be prepared by the steps of mixing thefuel, the emulsifier, the low molecular weight surfactant, and other oilsoluble additive using low shear techniques to form the fuel additivemixture. Then the fuel additive mixture is mixed with water andoptionally any desired water soluble additives to form the desiredemulsified water blended fuel.

[0040] In a batch process the water, the emulsifier, the surfactant, thefuel and optional additives are added to a tank, in the desired amounts.The mixture is emulsified using an emulsification device in the vessel,or alternatively the mixture flows from the vessel via a circular lineto the emulsification device which is external to the vessel, for about1 to about 20 tank turnovers. The temperature in the range of aboutambient temperature to about 212° F., and in another embodiment in therange of about 40° F. to about 150° F., and at a pressure in the rangeof about atmospheric pressure to about 10 atmospheres, in anotherembodiment about atmospheric pressure to about 80 psi, in anotherembodiment in the range of about 15 psi to about 30 psi.

[0041] The continuous process described herein depicts anotherembodiment of the invention. The feeds of the fuel, emulsifier,surfactant, water and optional additives are introduced as discretefeeds or in the alternative combinations of the discreet feeds. Theprocessing streams are introduced in or as close to the inlet of theemulsification device as possible. It is preferable that the emulsifieris added to the fuel as a fuel emulsifier stream prior to the discreetfeeds combining together. The continuous process generally occurs underambient conditions. The continuous process is generally done atatmospheric pressure to about 500 psi, in another embodiment in therange of about atmospheric pressure to about 120 psi, and in anotherembodiment in the range of about atmospheric pressure to about 50 psi.The continuous process generally occurs at ambient temperature. In oneembodiment the temperature is in the range of about ambient temperatureto about 212° F., and in another embodiment in the range of about 40° F.to about 150° F.

[0042] Alternatively, a concentrate is formed and all or substantiallyall the water, and water soluble additive and a portion of the fuel andall or substantially all the emulsifier and low molecular weightsurfactant is emulsified under low shear conditions to form aconcentrate fuel. The emulsified fuel, when used, is then blended undernormal mixing conditions with the remaining portion remaining portion ofthe fuel so that high speed emulsification conditions are not necessary.

[0043] The process may be in the form of a containerized equipment unitthat operates automatically. The process can be programmed and monitoredlocally at the site of its installation, or it can be programmed andmonitored from a location remote from the site of its installation. Thefully formulated water fuel blend is optionally dispensed to end usersat the installation site, or in another embodiment end users can blendthe concentrated emulsion with the final portion of fuel. This providesa way to make the water in fuel emulsions available to end users in widedistribution networks.

[0044] The emulsification may occur at high shear conditions that aregreater than 50,000 s⁻¹. However, the composition is emulsified at lowshear process conditions. The emulsification provides for the desiredparticle size and a uniform dispersion of water in the fuel and occursat a shear rate in the range of less than or equal to 50,000 s⁻¹, and inanother embodiment about 50,000 s⁻¹ to about 20,000 s⁻¹, and in anotherembodiment of about 20,000 s⁻¹ to about 1,000 s⁻¹, and in anotherembodiment less than 1,000 s⁻¹ to about 1 s⁻¹, and in another embodimentless than 100 s⁻¹ to about less than 1 s⁻¹ and in another embodimentless than 10 s⁻¹ to about less than 1 s⁻¹ shearing. If more than oneemulsification step is used, the shear rates of the emulsification stepscan be the same, similar or different, depending on the emulsifier andlow molecular weight surfactant used.

[0045] The emulsification occurs by any low shear method used in theindustry including but not limited to mixing, mechanical mixeragitation, static mixers, centrifugal pumps, positive displacementpumps, orifice plates, and the like. Examples of the devices include butare not limited to an Aquashear, pipeline static mixers, rotor/statormixers and the like. The Aquashear is a low-pressure hydraulic sheardevice. The Aquashear mixers are available from Flow ProcessTechnologies Inc.

[0046] The emulsification is able to occur at a low shear rate and doesnot require a high shear rate. By using a low shear rate, low energyprocess to make a stable and good emulsified water in oil blend/fuel oneuses less complex or simpler technology, equipment, devices and is morecost and/or time efficient.

EXAMPLE 1

[0047] About 0.3 parts by weight of glycerol monooleate and about 2.3parts by weight of a concentrate mixture containing about 23% wt 2300 MWPIB succinic acid/diethyl ethanolamine salt plus about 31% wt oleicacid/diethyl ethanol amine salt plus about 9.7% of about a 50% ammoniumnitrate solution and about 4.7% propylene glycol is mixed into about77.0 parts by weight of diesel fuel. This organic mixture is then co-fedwith about 20 parts by weight water through an 8.0 mm diameter SulzerSMX static mixer unit consisting of about 48 mixing elements at a totalvolumetric flow rate of about 470 millilitres per minute. The finalwhite emulsion was placed in storage bottles. After standing for onemonth at room temperature, about 99% of the material was still anemulsion. No banding or water was observed and only about 1% of thediesel fuel had separated. Particle size, oil separation, andsedimentation were found to be comparable to emulsifiers made using highshear mixing. The particle size of the emulsion was found to have a meanvolume diameter of less than about 1 micron. The storage bottles werestored at room temperature and observed at various time intervals. Itwas observed that the emulsion exhibited stability behavior equivalentto emulsions made using high shear conditions, i.e. about 3 part byvolume (pbv) of banded material at the bottom of the storage bottleafter 7 days and about 7 pbv after 28 days. In addition no free waterwas observed.

[0048] Fuel

[0049] The fuel comprises hydrocarbonaceous petroleum distillate fuel,non-hydrocarbonaceous materials that include but are not limited towater, oils, liquid fuels derived from vegetable sources, liquid fuelsderived from minerals and mixtures thereof. Suitable fuels include, butare not limited to, gasoline, diesel, kerosene, naphtha, aliphatics andparaffin. The fuel comprises non-hydrocarbonaceous materials include butis not limited to alcohols such as methanol, ethanol and the like,ethers such as diethyl ether, methyl ethyl ether and the like,organo-nitro compounds and the like; fuels derived from vegetable ormineral sources such as corn, alfalfa, shale, coal and the like. Thefuel also includes but is not limited to gas to liquid fuels. The fuelalso includes but is not limited to mixtures of one or morehydrocarbonaceous fuels and one or more non-hydrocarbonaceous materials.Examples of such mixtures are combinations of gasoline and ethanol andof diesel fuel and ether and the like.

[0050] In one embodiment, the fuel is any gasoline. Including, but notlimited to a chlorine-free gasoline or a low-chlorine gasoline, or a lowsulfur gasoline or sulfur-free gasoline and the like.

[0051] In one embodiment, the fuel is any diesel fuel. The diesel fuelsinclude, but are not limited to, those that contain alcohols and esters,has a sulfur content of up to about 0.05% by weight or sulfur-free, is achlorine-free or low-chlorine diesel fuel and the like.

[0052] The fuel is present in the emulsified fuel at a concentration ofabout 50% to about 95% by weight, and in one embodiment about 60% toabout 95% by weight, and in one embodiment about 65% to about 85% byweight, and in one embodiment about 80% to about 90% by weight of theemulsified fuel.

[0053] Water

[0054] The water used in the emulsified fuel may be taken from anysource. The water includes but is not limited to tap, deionized,demineralized, purified, for example, using reverse osmosis ordistillation, and the like. The water includes water mixtures thatfurther includes but are not limited to antifreeze components such asalcohols and glycols, ammonium salts such as ammonium nitrate, ammoniummaleate, ammonium acetate and the like, and combinations thereof; andother water soluble additives.

[0055] The water is present in the emulsified fuel at a concentration ofabout 1% to about 50% by weight, in one embodiment about 5% to about 40%being weight, in one embodiment about 5% to about 25% by weight, and inone embodiment about 10% to about 20% by weight of the emulsified fuel.

[0056] In another embodiment the water is present in the emulsified fuelat a concentration of less than 1% by weight, in another embodiment lessthan 0.5% by weight, in another embodiment less than 0.1% by weight, andin another embodiment in the range of about 0.1% to about 1% by weightof the emulsified fuel. An emulsified water in oil composition can bemade with water at these low levels with the fuel, the emulsifier, thesurfactant and optionally ammonium nitrate and in another embodimentwithout the surfactant and with the fuel, the emulsifier and optionallythe ammonium nitrate.

[0057] Emulsifier

[0058] The emulsifier includes but is not limited to

[0059] (i) at least one fuel-soluble product made by reacting at leastone hydrocarbyl-substituted carboxylic acid acylating agent with ammoniaor an amine including but not limited to alkanol amine, hydroxy amine,and the like, the hydrocarbyl substituent of said acylating agent havingabout 50 to about 500 carbon atoms;

[0060] (ii) a second acylating agent having at least one hydrocarbylsubstituents of up to about 40 carbon atoms, and reacting that saidacylating agent with ammonia or an amine;

[0061] (iii) at least one of an ionic or a nonionic compound having ahydrophilic-lipophilic balance (HLB) of about 1 to about 40;

[0062] (iv) mixture of (ii) or (iii) with (i) or a mixture of (i), (ii),and (iii);

[0063] (v) a water-soluble compound selected from the group consistingof amine salts, ammonium salts, azide compounds, nitrate esters,nitramine, nitrocompounds, alkali metal salts, alkaline earth metalsalts, in combination with (i), (ii), (iii), (v), (vii) or combinationsthereof;

[0064] (vi) the reaction product of polyacidic polymer with at least onefuel soluble product made by reacting at least onehydrocarbyl-substituted carboxylic acid acylating agent with ammonia, anamine, a polyamine, an alkanol amine or hydroxy amines;

[0065] (vii) an amino alkylphenol which is made by reacting analkylphenol, an aldehyde and an amine resulting in an amino alkylphenol;

[0066] (viii) a nitrogen free emulsifier; or

[0067] (ix) the combination of (i) through (viii) or combinationsthereof.

[0068] The emulsifier has at least one high molecular weight component.The emulsifier has a high molecular weight component relative to thesurfactant which has a low molecular weight.

[0069] The fuel-soluble product (i) of the emulsifier may be at leastone fuel-soluble product made by reacting at least onehydrocarbyl-substituted carboxylic acid acylating agent with ammonia oran amine including but not limited to alkanol amines, hydroxy amines,and the like, the hydrocarbyl substituent of said acylating agent havingabout 50 to about 500 carbon atoms, and is described in greater detailin U.S. Ser. No. 09/761,482, An Emulsifier For An Aqueous HydrocarbonFuel, incorporated by reference herein.

[0070] The hydrocarbyl-substituted carboxylic acid acylating agents maybe carboxylic acids or reactive equivalents of such acids. The reactiveequivalents may be acid halides, anhydrides, or esters, includingpartial esters and the like. The hydrocarbyl substituents for thesecarboxylic acid acylating agents may contain from about 50 to about 500carbon atoms, and in one embodiment about 50 to about 300 carbon atoms,and in one embodiment about 60 to about 200 carbon atoms. In oneembodiment, the hydrocarbyl substituents of these acylating agents havenumber average molecular weights of about 700 to about 3000, and in oneembodiment about 900 to about 2300.

[0071] In another embodiment, the fuel soluble product (i) of thepresent invention comprises an emulsifying amount of at least one of afuel-soluble hydrocarbyl-substituted carboxylic acylating agent and areaction product of said acylating agent with at least one of ammonia,an amine, an alcohol, a reactive metal, a reactive metal compound or amixture of two or more thereof, wherein the hydrocarbyl substituentcomprises a group derived from at least one polyolefin, said polyolefinhaving {overscore (M)}_(w)/{overscore (M)}_(n) greater than about 5.

[0072] The hydrocarbyl substituted acylating agents have a hydrocarbylgroup substituent that is derived from a polyolefin, with polydispersityand other features as described below. Generally, it has a numberaverage molecular weight of at least 600, 700, or 800, to 5000 or more,often up to 3000, 2500, 1600, 1300, or 1200. Typically, less than 5% byweight of the polyolefin molecules have {overscore (M)}_(n) less thanabout 250, more often the polyolefin has {overscore (M)}_(n) of at leastabout 800. The polyolefin preferably contains at least about 30%terminal vinylidene groups, more often at least about 60% and morepreferably at least about 75% or about 85% terminal vinylidene groups.The polyolefin has polydispersity, {overscore (M)}_(w)/{overscore(M)}_(n), greater than about 5, more often from about 6 to about 20. Thehydrocarbyl group is typically derived from a polyolefin or apolymerizable derivative thereof, including homopolymers andinterpolymers of olefin monomers having 2 to 30, to 6, or to 4 carbonatoms, and mixtures thereof. In a preferred embodiment the polyolefin ispolyisobutenyl.

[0073] Suitable olefin polymer hydrocarbyl groups, having suitablepolydispersity, can be prepared by heteropolyacid catalyzedpolymerization of olefins under conventional conditions. Preferredheteroplyacids include a phosphotungstic acid, a phosphomolybidc acid, asilicotungstic acid, a silicomolybdic acid and the like.

[0074] The hydrocarbyl-substituted carboxylic acid acylating agents maybe made by reacting one or more alpha-beta olefinically unsaturatedcarboxylic acid reagents containing 2 to about 20 carbon atoms,exclusive of the carboxyl groups, with one or more olefin polymers asdescribed more fully hereinafter. This reaction may occur under theconditions to add the alpha-beta olefinically unsaturated carboxylicacid reagents via a free radical addition process.

[0075] In one embodiment, the hydrocarbyl-substituted carboxylic acidacylating agent is a polyisobutene-substituted succinic anhydride, thepolyisobutene substituent having a number average molecular weight ofabout 1,500 to about 3,000, in one embodiment about 1,800 to about2,300, in one embodiment about 700 to about 1300, in one embodimentabout 800 to about 1000, said first polyisobutene-substituted succinicanhydride being characterized by about 1.3 to about 2.5, and in oneembodiment about 1.7 to about 2.1 In one embodiment, thehydrocarbyl-substituted carboxylic acid acylating agent is apolyisobutene-substituted succinic anhydride, the polyisobutenesubstituent having a number average molecular weight of about 1,500 toabout 3,000, and in one embodiment about 1,800 to about 2,300, saidfirst polyisobutene-substituted succinic anhydride being characterizedby about 1.3 to about 2.5, and in one embodiment about 1.7 to about 2.1,in one embodiment about 1.0 to about 1.3, and in one embodiment about1.0 to about 1.2 succinic groups per equivalent weight of thepolyisobutene substituent.

[0076] The fuel-soluble product (i) may be formed using ammonia, anamine and/or the metal bases of metals such as Na, K, Ca, and the like.The amines useful for reacting with the acylating agent to form theproduct (i) including but are not limited to, monoamines, polyamines,alkanol amines, hydroxy amines, and mixtures thereof, and amines may beprimary, secondary or tertiary amines.

[0077] Examples of primary and secondary monoamines include ethylamine,diethylamine, n-butylamine, di-n-butylamine, allylamine, isobutylamine,cocoamine, stearylamine, laurylamine, methyllaurylamine, oleylamine,N-methyloctylamine, dodecylamine, and octadecylamine. Suitable examplesof tertiary monoamines include trimethylamine, triethylamine,tripropylamine, tributylamine, monoethyldimethylamine,dimethylpropylamine, dimethylbutylamine, dimethylpentylamine,dimethylhexylamine, dimethylheptylamine, and dimethyloctylamine.

[0078] The amines include but are not limited to hydroxyamines, such asmono-, di-, and triethanolamine, dimethylethanol amine, diethylethanolamine, di-(3-hydroxy propyl) amine, N-(3-hydroxybutyl) amine,N-(4-hydroxy butyl) amine, and N,N-di-(2-hydroxypropyl) amine; alkylenepolyamines such as methylene polyamines, ethylene polyamines, butylenepolyamines, propylene polyamines, pentylene polyamines, and the like.Specific examples of such polyamines include ethylene diamine,diethylene triamine, triethylene tetramine, propylene diamine,trimethylene diamine, tripropylene tetramine, tetraethylene pentamine,hexaethylene heptamine, pentaethylene hexamine, or a mixture of two ormore thereof; ethylene polyamine bottoms or a heavy polyamine. Thefuel-soluble product (i) may be a salt, an ester, an ester/salt, anamide, an amide, or a combination of two or more thereof.

[0079] The fuel-soluble product (i) may be present in the water fuelemulsion at a concentration of up to about 15% by weight based on theoverall weight of the emulsion, and in one embodiment about 0.1 to about15% by weight, and an one embodiment about 0.1 to about 10% by weight,and in one embodiment about 0.1 to about 5% by weight, and in oneembodiment about 0.1 to about 2% by weight, and in one embodiment about0.1 to about 1% by weight, and in one embodiment about 0.1 to about 0.7%by weight.

[0080] The second acylating agent (ii) of this invention includescarboxylic acids and their reactive equivalents such as acid halides andanhydrides.

[0081] In one embodiment, the carboxylic acid is a monocarboxylic acidof about 1 to about 35 carbon atoms, and in one embodiment about 16 toabout 24 carbon atoms. Examples of these monocarboxylic acids includelauric acid, oleic acid, isostearic acid, palmitic acid, stearic acid,linoleic acid, arachidic acid, gadoleic acid, behenic acid, erucic acid,tall oil fatty acids, lignoceric acid and the like. These acids may besaturated, unsaturated, or have other functional groups, such as hydroxygroups, as in 12-hydroxy stearic acid, from the hydrocarbyl backbone.

[0082] In one embodiment, the carboxylic acid is ahydrocarbyl-substituted succinic acid represented correspondingly by theformula

[0083] wherein formula R is hydrocarbyl group of about 12 to about 35,and in one embodiment from about 12 to about 30, and in one embodimentfrom about 16 to about 24 and in one embodiment from about 26 to about35 carbon atoms. The production of such hydrocarbyl-substituted succinicacids or anhydrides via alkylation of maleic acid or anhydride or itsderivatives with a halohydrocarbon or via reaction of maleic acid oranhydride with an olefin polymer having a terminal double bond is knownto those of skill in the art.

[0084] In one embodiment, the acylating agent (ii) is a carboxylic acidor the acylating agent (ii) used to prepare carboxylic acid and is madeby reacting one or more alpha-beta olefinically unsaturated carboxylicacid reagents containing about 2 to about 20 carbon atoms, exclusive ofthe carboxyl based groups, with one or more olefin polymers containingat least about 16 carbon atoms.

[0085] In the one embodiment, the ratio of the first acylating agent(i), to the second acylating agent (ii) in the emulsified fuel is in therange of about 9:1 to about 1:9; in another embodiment in the range ofabout 5:1 to about 1:5; and in another embodiment in the range of about1:3 to about 3.1.

[0086] The ionic or nonionic compound (iii) of the emulsifier has ahydrophilic-lipophilic balance (HLB, which refers to the size andstrength of the polar (hydrophilic) and non-polar (lipophilic) groups onthe surfactant molecule) in the range of about 1 to about 40, and in oneembodiment about 4 to about 15 and is described in greater detail inU.S. Ser. No. 09/761,482, An Emulsifier For An Aqueous Hydrocarbon Fuel,incorporated by reference herein. Examples of these compounds aredisclosed in McCutcheon's Emulsifiers and Detergents, 1998, NorthAmerican & International Edition. Pages 1-235 of the North AmericanEdition and pages 1-199 of the International Edition are incorporatedherein by reference for their disclosure of such ionic and nonioniccompounds having an HLB in the range of about 1 to about 40, in oneembodiment about 1 to about 30, in one embodiment about 1 to 20, and inanother embodiment about 1 to about 10. Examples include low molecularweight variants of (i) or (vii) such as those having a hydrocarbon groupin the range of C₈ or C₂₀. Useful compounds include alkanolamines,carboxylates including amine salts, metallic salts and the like,alkylarylsulfonates, amine oxides, poly(oxyalkylene) compounds,including block copolymers comprising alkylene oxide repeat units,carboxylated alcohol ethoxylates, ethoxylated alcohols, ethoxylatedalkylphenols, ethoxylated amines and amides, ethoxylated fatty acids,ethoxylated fatty esters and oils, fatty esters, fatty acid amides,including but not limited to amides from tall oil fatty acids andpolyamides, glycerol esters, glycol esters, sorbitan esters, imidazolinederivatives, lecithin and derivatives, lignin and derivatives,monoglycerides and derivatives, olefin sulfonates, phosphate esters andderivatives, propoxylated and ethoxylated fatty acids or alcohols oralkylphenols, sorbitan derivatives, sucrose esters and derivatives,sulfates or alcohols or ethoxylated alcohols or fatty esters, sulfonatesof dodecyl and tridecyl benzenes or condensed naphthalenes or petroleum,sulfosuccinates and derivatives, and tridecyl and dodecyl benzenesulfonic acids.

[0087] The emulsifier (iv) may be a mixture of (i) and (ii) describedabove and is further described in detail in U.S. Ser. No. 09/761,482, AnEmulsifier For An Aqueous Hydrocarbon Fuel, incorporated by referenceherein.

[0088] The emulsifier of the water-soluble compound (v) may be an aminesalt, ammonium salt, azide compound, nitro compound, nitrate salts,alkali metal salt, alkaline earth metal salt, or mixtures of two or morethereof and is described in greater detail in U.S. Ser. No. 09/761,482,An Emulsifier For An Aqueous Hydrocarbon Fuel, incorporated by referenceherein. These compounds are distinct from the fuel-soluble product (i)and the ionic or nonionic compound (ii) discussed above. Thesewater-soluble compounds include organic amine nitrates, nitrate esters,azides, nitramines and nitro compounds. Also included are alkali andalkaline earth metal carbonates, sulfates, sulfides, sulfonates, and thelike. In another embodiment the water soluble compound is in the form ofa salt, such as an amine salt, ammonia salt, azide salt, alkali metalsalt, alkaline earth metal salt, nitrate salt and mixtures thereof.

[0089] Particularly useful are the amine or ammonium salts such asammonium nitrate, ammonium acetate, methylammonium nitrate,methylammonium acetate, hydroxy ammonium nitrate, ethylene diaminediacetate; urea nitrate; urea; guanidinium nitrate; and combinationsthereof. However, these ammonium salts of the emulsifier, if used areindependent of and distinct and separate from the aqueous organicammonium salt compound of the emulsified fuel discussed above.

[0090] In one embodiment the emulsifier (vi) is the reaction product ofA) a polyacidic polymer, B) at least one fuel soluble product made byreacting at least one hydrocarbyl-substituted carboxylic acid acylatingagent, and C) a hydroxy amine and/or a polyamine and is described ingreater detail in U.S. Ser. No. 09/761,482, An Emulsifier For An AqueousHydrocarbon Fuel, incorporated by reference herein.

[0091] The polyacidic polymers used in the reaction include but are notlimited to C₄ to C₃₀; preferably C₈ to C₂₀ olefin/maleic anhydridecopolymers; maleic anhydride/styrene copolymers; poly-maleic anhydride;acrylic and methacrylic acid containing polymers; poly-(alkyl)acrylates;reaction products of maleic anhydride with polymers with multiple doublebonds;

[0092] A copolymer of an olefin and a monomer having the structure:

[0093] wherein X and X1 are the same or different provided that at leastone of X and X₁ is such that the copolymer can function as a carboxylicacylating agent; and combinations therein.

[0094] The emulsifier produced from the reaction product of thepolyacidic polymer with the fuel soluble product (i) comprises about 25%to about 95% of fuel soluble product and about 0.1% to about 50% of thepolyacidic polymer; preferably about 50% to about 92% fuel solubleproduct and about 1% to about 20% of the polyacidic polymer, and mostpreferably about 70% to about 90% of fuel soluble product and about 5%to about 10% of the polyacidic polymer. In one embodiment the emulsifieris described as a polyalkenyl succinimide crosslinked with anolefin/maleic anhydride copolymer.

[0095] The amino alkyl emulsifier (vii) is comprised of the reactionproduct of an amino alkylphenol, an aldehyde, and an amine resulting inamino alkylphenol. The amino alkylphenol can be made by (a) the reactionof alkylphenol directly with an aldehyde and an amine resulting in analkylphenol monomer connected by a methylene group to an amine, (b) thereaction of an alkylphenol with an aldehyde resulting in an oligomerwherein the alkylphenols are bridged with methylene groups, the oligomeris then reacted with more aldehyde and an amine to give a Mannichproduct, or (c) a mixture of (a) and (b) and is described in greaterdetail in U.S. Ser. No. 09/977,747 entitled A Continuous Process ForMaking An Aqueous Hydrocarbon Fuel Emulsion incorporated by referenceherein.

[0096] The alkylphenols have an alkyl group selected from C₁ to C₂₀₀,preferably C₆ to C₁₇₀ wherein the alkyl group is either linear, branchedor a combination thereof. The alkylphenols include, but are not limitedto, polypropylphenol, polybutylphenol, poly(isobutenyl)phenol,polyamylphenol, tetrapropylphenol, similarly substituted phenols and thelike. The preferred alkylphenols are tetrapropenylphenol andpoly(isobutenyl)phenol.

[0097] The aldehydes include, but are not limited to, aliphaticaldehydes, such as formaldehyde; acetaldehyde; aldol (β-hydroxybutyraldehyde); aromatic aldehydes, such as benzaldehyde; heterocyclicaldehydes, such as furfural, and the like. The aldehyde may contain asubstituent group such as hydroxyl, halogen, nitro and the like; inwhich the substituent does not take a major part in the reaction. Thepreferred aldehyde is formaldehyde.

[0098] The amines are those which contain an amino group characterizedby the presence of at least one active hydrogen atom. The amines may beprimary amino groups, secondary amino groups, or combinations of primaryand secondary amino groups.

[0099] The amines include, but are not limited to, alkanolamines; di-and polyamine (polyalkyene amines); polyalkyl polyamines;propylenediamine, the aromatic amines such as o-, m- and p-phenylenediamine, diamino naphthalenes; the acid-substituted polyalkylpolyamines,and the corresponding formyl-, propionyl-, butyryl-, and the likeN-substituted compounds; and the corresponding cyclized compounds formedtherefrom, such as the N-alkyl amines of imidazolidine and pyrimidine.Substituent groups attached to the carbon atoms of these amines aretypified by alkyl, aryl, alkaryl, aralkyl, cycloalkyl, and aminocompounds. The amino alkylphenols emulsifier of this invention may bemade by reacting the alkylphenol:aldehyde:amine in a ratio range of1:1:0.1 molar to 1:2:2 molar, in one embodiment preferably 1:0.9:0.1 to1:1.9:1.9, in one embodiment preferably 1:1.5:1.2 molar to 1:1.9:1.8molar, and in one embodiment preferably 1:0.8:0.3 to 1:1.5:0.7,resulting in the amino alkylphenol emulsifier. In another embodiment ofthis invention the amino alkylphenol is made by the reaction of analkylphenol with an aldehyde, resulting in an oligomer wherein thealkylphenols are bridged with methylene groups; then the oligomer isreacted with more aldehyde and amine to give the emulsifier Mannichproduct of this invention. The reaction is prepared by any known methodsuch as an emulsion, a solution, a suspension, and a continuous additionbulk process. The reaction is carried out under conditions that providefor the formation of the desired product.

[0100] The nitrogen-free emulsifier (viii) comprises:

[0101] (viii)(a) a hydrocarbyl substituted carboxylic acid, or areaction product of the hydrocarbyl substituted carboxylic acid or areactive equivalent of such acid with an alcohol, the hydrocarbylsubstituent of the acid or reactive equivalent thereof containing atleast about 30 carbon atoms; and

[0102] (viii)(b) at least one compound represented by one or more of theformulae:

[0103]  wherein each R is independently hydrogen or a hydrocarbyl groupof up to about 60 carbon atoms; each R′ and R″ is independently analkylene group of 1 to about 20 carbon atoms; each R′″ is independentlyhydrogen, or an acyl or hydrocarbyl group of up to about 30 carbonatoms; n is a number in the range of zero to about 50; and x, y and zare independently numbers in the range of zero to about 50 with thetotal for x, y and z being at least 1. This emulsifier is furtherdisclosed in Applicants U.S. application entitled “Water Blended FuelComposition”, Applicants' reference number 3134, U.S. Ser. No. ______,incorporated by reference herein.

[0104] The emulsifier component (viii) (a) may be a hydrocarbylsubstituted carboxylic acid, or a reaction product of the hydrocarbylsubstituted carboxylic acid or a reactive equivalent thereof with analcohol. The carboxylic acids may be monobasic or polybasic. Thepolybasic acids include dicarboxylic acids, although tricarboxylic andtetracarboxylic acids may be used. The reactive equivalents may be acidhalides, (e.g., chlorides), anhydrides or esters, including partialesters, and the like.

[0105] The alcohol which may be reacted with the hydrocarbyl substitutedcarboxylic acid or reactive equivalent to form emulsifier component(iii)(a) may be a mono- or a polyhydric hydrocarbon-based alcohol suchas methanol, ethanol, the propanols, butanols, pentanols, hexanols,heptanols, octanols, decanols, and the like. Also included are fattyalcohols and mixtures thereof, including saturated alcohols such aslauryl, myristyl, cetyl, stearyl and behenyl alcohols, and unsaturatedalcohols such as palmitoleyl, oleyl and eicosenyl. Higher syntheticmonohydric alcohols of the type formed by the Oxo process (e.g.,2-ethylhexanol), by the aldol condensation, or byorganoaluminum-catalyzed oligomerixation of alpha-olefins (e.g.,ethylene), followed by oxidation, may be used. Alicyclic analogs of theabove-described alcohols may be used; examples include cyclopentanol,cyclohexanol, cyclododecanol, and the like.

[0106] The polyhydroxy compounds that may be used include ethylene,propylene, butylene, pentylene, hexylene and heptylene glycols; tri-,tetra-, penta-, hexa- and heptamethylene glycols andhydrocarbon-substituted analogs thereof (e.g., 2-ethyl-1,3-trimethyleneglycol, neopentyl glycol, etc.), as well as polyoxyalkylene compoundssuch as diethylene and higher polyethylene glycols, tripropylene glycol,dibutylene glycol, dipentylene glycol, dihexylene glycol and diheptyleneglycol, and their monoethers. A glycol that may be used is 1,2-propanediol.

[0107] Phenol, naphthols, substituted phenols (e.g., the cresols), anddihydroxyaromatic compounds (e.g., resorcinol, hydroquinone), as well asa benzyl alcohol and similar di-hydroxy compounds wherein the secondhydroxy group is directly bonded to an aromatic carbon (e.g., 3-HOφCH₂OHwherein φ is a divalent benzene ring) may be used. Sugar alcohols of thegeneral formula HOCH₂ (CHOH)₁₋₅ CH₂OH such as glycerol, sorbitol,mannitol, and the like, and their partially esterified derivatives maybe used. Oligomers of such sugar alcohols, including diglycerol,triglycerol, hexaglycerol, and the like, and their partially esterfiedderivatives may be used. Methylol polyols such as pentaerythritol andits oligomers (di- and tripentaerythritol, etc.), trimethylolethane,trimethylolpropane, and the like may be used.

[0108] The emulsifier component (viii)(a) may be in the form of an acid,an ester, or a mixture thereof. The acid may be formed by reacting ahydrocarbyl substituted carboxylic acid reactive equivalent with waterto provide the desired acid. For example, hydrocarbyl (e.g.,polyisobutene) substituted succinic anhydride may be reacted with waterto form hydrocarbyl substituted succinic acid. The reaction between thehydrocarbyl substituted carboxylic acid or reactive equivalent thereofand the alcohol to form an ester may be carried out under suitable esterforming reaction conditions. In one embodiment, the hydrocarbylsubstituted carboxylic acid or reactive equivalent thereof and thealcohol are reacted in amounts sufficient to provide from about 0.3 toabout 3 equivalents of the acid or reactive equivalent thereof perequivalent of alcohol. In one embodiment, this ratio is from about 0.5:1to about 2:1.

[0109] The emulsifier component (viii)(b) may be at least one compoundrepresented by one or more of the formulae:

[0110] wherein each R is independently hydrogen or a hydrocarbyl groupof up to about 60 carbon atoms; each R′ and R″ is independently analkylene group of 1 to about 20 carbon atoms; each R′″ is independentlyhydrogen, or an acyl or hydrocarbyl group of up to about 30 carbonatoms; n is a number in the range of zero to about 50; and x, y and zare independently numbers in the range of zero to about 50 with thetotal for x, y and z being at least 1. In the above formulae, R may be ahydrocarbyl group of about 6 to about 60 carbon atoms, and in oneembodiment abut 6 to about 45 carbon atoms, and in one embodiment about6 to about 30 carbon atoms, and in one embodiment about 14 to about 30carbon atoms. In one embodiment, R may be a hydrocarbyl group of about 9to about 11 carbon atoms. R′ and R″ may be independently alkylene groupsof about 1 to about 6 carbon atoms, and in one embodiment about 1 toabout 4 carbon atoms. In one embodiment, R′ is an alkylene groupcontaining about 2 to about 3 carbon atoms, and in one embodiment about2 carbon atoms. In one embodiment, R″ is an alkylene group containing 1carbon atom. R′″ may be an acyl or hydrocarbyl group of 1 to about 30carbon atoms, and in one embodiment 1 to about 24 carbon atoms, and inone embodiment 1 to about 18 carbon atoms, and in one embodiment 1 toabout 12 carbon atoms, and in one embodiment 1 to about 6 carbon atoms.n may be a number in the range of 1 to about 50, and in one embodiment 1to about 30, and in one embodiment 1 to about 20, and in one embodiment1 to about 12, and in one embodiment about 4 to about 10, and in oneembodiment about 5 to about 10, and in one embodiment about 5 to about8, and in one embodiment about 5 or about 6. x, y and z may beindependently numbers in the range of zero to about 50, and in oneembodiment zero to about 30, and in one embodiment zero to about 10;with the total of x, y and z being at least 1, and in one embodiment inthe range of 1 to about 50, and in one embodiment 10 to about 40, and inone embodiment 20 to about 30, and in one embodiment about 25.

[0111] Examples of compounds represented by formula (viii-b-1) that maybe used include: C₉-C₁₁ alkoxy poly (ethoxy)₈ alcohol; C₁₂-C₁₅ alkoxypoly (isopropoxy)₂₂₋₂₆ alcohol; oleyl alcohol pentaethoxylate; and thelike.

[0112] Examples of compounds represented by formula (viii-b-2) that maybe used include diglycerol monooleate, diglycerol monosteaate,polyglycerol monooleate, and the like.

[0113] Examples of compounds represented by formula (viii-b-3) that maybe used include polyethylene glycol (Mn=200) distearate, polyethyleneglycol (Mn=400) distearate, polyethylene glycol (Mn=200) dioleate,polyethylene glycol (Mn=400) soya bean oil ester, and the like.

[0114] Examples of compounds represented by formula (viii-b-4) that maybe used include glycerol monooleate, diglycerol dioleate, diglyceroldistearate, polyglycerol dioleate, and the like.

[0115] Examples of compounds represented by formula (viii-b-5) that maybe used include sorbitan monooleate, sorbitan monoisostearate, sorbitansesquioleate, and sorbitan trioleate, and the like.

[0116] Examples of compounds represented by formula (viii-b-6) that maybe used include polyethoxy glycerol trioleate wherein the compoundcontains 25 ethoxy groups.

[0117] In one embodiment, the emulsifier (viii)(b) is an alkoxypolyethoxy alcohol wherein the alkoxy group contains about 14 to about30 carbon atoms and the polyethoxy group contains up to about 10 ethoxygroups, and in one embodiment about 5 to about 10 ethoxy groups, and inone embodiment about 5 or 6 ethoxy groups.

[0118] In one embodiment, the emulsifier (viii)(b) is an alkoxypolyethoxy alcohol wherein the alkoxy group contains about 9 to about 11carbon atoms and the polyethoxy group contains about 8 ethoxy groups. Anoptional acid component that may be used in one embodiment with thenitrogen free emulsifier and in another embodiment with each of theemulsifiers alone or in combinations may be used in the inventive fuelcomposition comprises one or more acids having a pKa of up to about 6,and in one embodiment up to about 5, and in one embodiment up to about4, and in one embodiment from about 0 to about 4, and in one embodimentabout 1 to about 3.5, and in one embodiment about 1.5 to about 3. Thisacid component includes but is not limited too carboxylic acid, formicacid, acetylenedicarboxylic acid, benzenehexacarboxylic acid,benzenepentacarboxylic acid, benzenetetracarboxylic acid,benzenetricarboxylic acid, 2-butyn-1,4-dioic acid, 2-butynoic acid,citraconic acid, cyclopropane-1,1-dicarboxylic acid,2,6-dihydroxybenzoic acid, dihydroxymaleic acid, dihydroxymalic acid,dihydroxytatric acid, alpha, alpha-dimethyloxaloacetic acid,dipropylmalonic acid, ethylene oxide dicarboxylic acid, hydroxyasparticacid, maleic acid, 2-oxobutanoic acid, triethylsuccinic acid, citricacid, tartaric acid, glyoxylic acid, oxalic acid, lactic acid,oxomalonic acid (mesoxalic acid), and mixtures thereof.

[0119] When used, this acid component may function as an ionizing agent.The concentration of this acid component in the water blended fuelcomposition may range up to about 5 percent by weight, and in oneembodiment from about 0.001 to about 3 percent by weight, and in oneembodiment about 0.01 to about 1 percent by weight.

[0120] Other Additives

[0121] In one embodiment, the emulsified fuel contains a cetaneimprover. The cetane improvers that are useful include but are notlimited to peroxides, nitrates, nitrites, nitrocarbamates, and the like.Useful cetane improvers include but are not limited to nitropropane,dinitropropane, tetranitromethane, 2-nitro-2-methyl-1-butanol,2-methyl-2-nitro-1-propanol, and the like. Also included are nitrateesters of substituted or unsubstituted aliphatic or cycloaliphaticalcohols which may be monohydric or polyhydric. These includesubstituted and unsubstituted alkyl or cycloalkyl nitrates having up toabout 10 carbon atoms, and in one embodiment about 2 to about 10 carbonatoms. The alkyl group may be either linear or branched, or a mixture oflinear or branched alkyl groups. Examples include methyl nitrate, ethylnitrate, n-propyl nitrate, isopropyl nitrate, allyl nitrate, n-butylnitrate, isobutyl nitrate, sec-butyl nitrate, isooctyl nitrate,tert-butyl nitrate, n-amyl nitrate, isoamyl nitrate, 2-amyl nitrate,3-amyl nitrate, tert-amyl nitrate, n-hexyl nitrate, n-heptyl nitrate,n-octyl nitrate, 2-ethylhexyl nitrate, sec-octyl nitrate, n-nonylnitrate, n-decyl nitrate, cyclopentyl nitrate, cyclohexyl nitrate,methylcyclohexyl nitrate, and isopropylcyclohexyl nitrate. Also usefulare the nitrate esters of alkoxy-substituted aliphatic alcohols such as2-ethoxyethyl nitrate, 2-(2-ethoxy-ethoxy) ethyl nitrate,1-methoxypropyl-2-nitrate, 4-ethoxybutyl nitrate, etc., as well as diolnitrates such as 1,6-hexamethylene dinitrate. A useful cetane improveris 2-ethylhexyl nitrate.

[0122] The concentration of the cetane improver in the emulsified fuelis at any concentration sufficient to provide the emulsion with thedesired cetane number. In one embodiment, the concentration of thecetane improver is at a level of up to about 10% by weight, and in oneembodiment about 0.05% to about 10% by weight, and in one embodimentabout 0.05% to about 5% by weight, and in one embodiment about 0.05% toabout 1% by weight of the emulsified fuel.

[0123] In addition to the foregoing materials, other fuel additives thatknown to those skilled in the art may be used in the emulsified fuel.These include but are not limited to dyes, rust inhibitors such asalkylated succinic acids and anhydrides, bacteriostatic agents, guminhibitors, metal deactivators, upper cylinder lubricants and the like.

[0124] The total concentration of the additives, in the emulsified fuelis from about 0.05% to about 30% by weight, and in one embodiment about0.1% to about 20% by weight, and in one embodiment about 0.1% to about15% by weight, and in one embodiment about 0.1% to about 10% by weight,and in one embodiment about 0.1% to about 5% by weight of the emulsifiedfuel.

[0125] The additives, including the foregoing emulsifiers, may bediluted with a substantially inert, normally liquid organic solvent suchas naphtha, benzene, toluene, xylene or diesel fuel to form an additiveconcentrate which is then mixed with the fuel and water to form theemulsified fuel.

[0126] The emulsified fuel may contain up to about 60% by weight organicsolvent, and in one embodiment about 0.01% to about 50% by weight, andin one embodiment about 0.01% to about 20% by weight, and in oneembodiment about 0.1% to about 5% by weight, and in one embodiment about0.1% to about 3% by weight of the emulsified fuel.

[0127] The emulsified fuel may additionally contain an antifreeze agent.The antifreeze agent is typically an alcohol. Examples include but arenot limited to ethylene glycol, propylene glycol, methanol, ethanol,glycerol and mixtures of two or more thereof. The antifreeze agent istypically used at a concentration sufficient to prevent freezing of thewater used in the water fuel emulsion. The concentration is thereforedependent upon the temperature at which the fuel is stored or used. Inone embodiment, the concentration is at a level of up to about 20% byweight of the emulsified fuel, and in one embodiment about 0.1% to about20% by weight, and in one embodiment about 1% to about 10% by weight ofthe emulsified fuel.

[0128] Engines

[0129] The engines that may be operated in accordance with the inventioninclude all (internal combustion) engines including spark ignited(gasoline) and compression ignited (diesel) for both mobile includinglocomotive, marine, automotive, truck, heavy duty, aviation and thelike, and stationary power plants. The engines may be two-cycle orfour-cycle. The engines may employ conventional after treatment devices.Included are on- and off-highway engines, including new engines as wellas in-use engines.

[0130] An open-flame burning apparatus may be operated with theemulsified water fuel blend of the invention. The open-flame burningapparatus may be any open-flame burning apparatus equipped to burn aliquid fuel. These include domestic, commercial and industrial burners.The industrial burners include those requiring preheating for properhandling and atomization of the fuel. Also included are oil firedcombustion units, oil fired power plants, fired heaters and boilers, andboilers for use in ships including deep draft vessels. The fuel burningapparatus may be a boiler for commercial applications included areboilers for power plants, utility plants, and large stationary andmarine engines. The open-flame fuel burning apparatus may be anincinerator or a rotary kiln incinerator, liquid injection kiln,fluidized bed kiln, cement kiln, and the like. Also included are steeland aluminium forging furnaces. The open-flame burning apparatus may beequipped with a flue gas recirculation system.

[0131] From the above description and examples the invention thoseskilled in the art may perceive improvements, changes and modificationsin the invention. Such improvement changes and modifications areintended to be covered by the appended claims.

What is claimed:
 1. An emulsified water in oil composition comprising:A) a fuel; B) a water; C) a high molecular weight emulsifier; D) asurfactant having a molecular weight of about less than or equal toabout 950 g/mol wherein the surfactant comprises: i) natural fats; ii)non-ionic and ionic surfactants; iii) co-surfactanta; iv) fatty acidsand their amine salts; or v) combinations thereof; and E) optionallyammonium nitrate.
 2. The composition of claim 2 wherein a fuel is in therange of about 50% to about 99% by weight of the composition; the wateris in the range of about 1% to about 50% by weight of the composition;the emulsifier is in the range of about 1% to about 50% by weight of thecomposition; and the surfactant in the range of about 0.001% to about15% by weight of the composition.
 3. The composition of claim 2 whereina fuel is in the range of about 50% to about 99% by weight of thecomposition; the water is in the range of less than 1% by weight of thecomposition; the emulsifier is in the range of about 1% to about 50% byweight of the composition; and the surfactant in the range of about0.001% to about 15% by weight of the composition.
 4. The composition ofclaim 1 wherein the fuel is a diesel fuel.
 5. The composition of claim 1wherein the water in oil composition is an emulsified water blended fueland wherein the fuel is selected from the group consisting of petroleumdistillate fuel such as diesel, gasoline, fuel oil a mixture thereof; afuel derived from vegetables, corn, alfalfa, rapeseed, soybeans, shale,coal or mixtures thereof; a biodegradable fuel; biodiesel; residualfuel; bitumen; alcohol; ether; ethanol; Fischer-Tropsch fuels; andcombinations thereof.
 6. The composition of claim 1 wherein thesurfactant has a low molecular weight in the range of about 900 g/mol toabout 30 g/mol.
 7. The composition of claim 1 wherein the surfactant hasa low molecular weight in the range of about 400 g/mol to about 90g/mol.
 8. The composition of claim 1 wherein the surfactant is in therange of about 0.01% to about 10% by weight of the water in oilcomposition.
 9. The composition of claim 1 wherein the natural fatsurfactant is selected from the group consisting of triglycerides,hydrolyzed triglycerides, oxidized products of triglycerides, vegetableoils, refined vegetable oils, used vegetable oils and combinationsthereof.
 10. The composition of claim 1 wherein the non ionic and ionicsurfactants are selected from the group consisting of alkyl ethoxylates,ethoxylated alkylphenols, alkyl glucosides, ethoxylated alcohols,ethoxylated amines, ethoxylatedamides amides derived from fatty acids,amides derived from fatty alcohols, ethers alcohols, fatty alcohols,esters of fatty acids ethers of fatty acides, esters of fatty alcoholsand combinations thereof.
 11. The composition of claim 1 wherein thenon-ionic and ionic surfactants have a hydrophilic lipophilic balance(HLB) in the range of about 2 to about
 40. 12. The composition of claim11 wherein the non-ionic and ionic surfactants are selected from thegroup consisting of alkanolamides, alkylarylsulfonates, amine oxides,poly(oxyalkylene) compounds, including block copolymers comprisingalkylene oxide repeat units (Pluronic™), carboxylated alcoholethoxylates, such as fatty esters, glycerol esters, glycol esters,imidazoline derivatives, lecithin and derivatives, lignin andderivatives, monoglycerides and diglycerides and derivatives, phosphateesters and derivatives, propoxylated fatty acids, propoxylated fattyalcohols, alkyl phenols, sorbitan derivatives, sucrose esters,derivatives of sucrose esters, sulfates or alcohols or ethoxylatedalcohols or fatty esters, sulfonates of dodecyl aoxtridecyl benzenes orcondensed naphthalenes, and combinations thereof.
 13. The composition ofclaim 8 wherein the non-ionic and ionic surfactants are selected fromthe group consisting of C12-C14 alcohol with two ethoxylates, ethomeenC12, Neodol 25-3, oleylic alcohol with 5 ethoxylates,(nonylphenoxypoly(ethyleneoxy) ethanol, nonoxynol-8),(a-(4-nonylphenyl)-∞-hydroxypoly(oxy-1,2-ethanediyl), alcoholethoxylates, sorbitan monooleate, sorbitan monoisostearate, glyceroldioleate, glycerol monooleate, lauric acid, myristic acid, coconut acid,coconut oil, oleic acid, tall oil fatty acid, linoleic acid, soybeanoil, apricot kernel oil, wheat germ oil, monocarboxylic fatty acids,triglycerides, and combinations thereof.
 14. The composition of claim 1wherein the co-surfactant is selected from the group consisting ofalcohols, amines, amides, ketones, esters, ethers and combinationsthereof and further wherein the co-surfactant has from about 1 to about24 carbon atoms.
 15. The composition of claim 14 wherein the alcoholsare selected from the group consisting of propylene glycol, ethyleneglycol, isopropanol, 2 ethyl hexanol, stearyl alcohol, oleyl alcoholmethanol, ethanol and combinations thereof.
 16. The composition of claim1 wherein the fatty acids and their amine salt surfactants are selectedfrom the group consisting of diethyl ethanolamine salts of oleic acid,tall oil fatty acids, stearic acid, palmitic acid, lauric acid andcombinations thereof.
 17. A process for making a water in oilcomposition comprising shearing; A) a fuel in the range of about 50% toabout 99% by weight of the composition; B) a water in the range of about1% to 50% by weight of the composition; C) a high molecular weightemulsifier in the range of about 1% to about 50% by weight of thecomposition; D) a low molecular weight surfactants in the range of about0.001% to about 15% by weight of the composition wherein the surfactantcomprises natural fats, non ionic surfactants, co-surfactant havingabout 1 to 24 carbon atoms; fatty acids and their amine salts; andcombinations thereof and wherein the shearing mixing occurs at a shearrate in the range of less than or equal to 50,000 s⁻¹; and E) optionallyammonium nitrate.
 18. The process of claim 17 wherein the shear rate inthe range of about 20,000 s⁻¹ to about 1 s⁻¹.
 19. The process of claim17 wherein the shear rate is in the range of about 1,000 s⁻¹ to about 1s⁻¹.
 20. The process of claim 17 wherein the water in oil composition isan emulsified water in fuel and wherein the fuel is selected from thegroup consisting of petroleum distillate fuel such as diesel, gasoline,fuel oil a mixture thereof, a fuel derived from vegetables, corn,alfalfa, rapeseed, soybeans, shale, coal or mixtures thereof, abiodegradable fuel, biodiesel, residual fuel, bitumen, alcohol, ether,ethanol and combinations thereof.
 21. The composition of claim 1 whereinthe emulsifier is selected from the group consisting of A) at least onefuel-soluble product made by reacting at least onehydrocarbyl-substituted carboxylic acid acylating agent with ammonia oran amine including but not limited to alkanol amine, hydroxy amine, andthe like, the hydrocarbyl substituent of said acylating agent havingabout 50 to about 500 carbon atoms; B) a second acylating agent havingat least one hydrocarbyl substituents of up to about 40 carbon atoms,and reacting that said acylating agent with ammonia or an amine; C) awater-soluble compound selected from the group consisting of aminesalts, ammonium salts, azide salt, nitrate ester salt, alkali metalsalts, alkaline earth metal salts or mixtures thereof in combinationwith A, B, D, E, F or G; D) the reaction product of polyacidic polymerwith at least one fuel soluble product made by reacting at least onehydrocarbyl-substituted carboxylic acid acylating agent with ammonia, anamine, a polyamine, an alkanol amine or hydroxy amines; E) an aminoalkylphenol which is made by reacting an alkylphenol, an aldehyde and anamine resulting in an amino alkylphenol; F) nitrogen free emulsifier; orG) the combination of (A), (B), (C), (D), (E), (F) or combinationsthereof.
 22. The composition claim 1 wherein the water in oilcomposition is an emulsified fuel used to operate an apparatus selectedfrom the group consisting of an engine, an open flame burner, and aninternal combustion engines.
 23. A process for making a water in oilcomposition comprising shearing; A) a fuel in the range of about 50% toabout 99% by weight of the composition; B) a water in the range of lessthan about 1% by weight of the composition; C) a high molecular weightemulsifier in the range of about 1% to about 50% by weight of thecomposition; D) a low molecular weight surfactants in the range of about0.001% to about 15% by weight of the composition wherein the surfactantcomprises natural fats, non ionic surfactants, co-surfactant havingabout 1 to 24 carbon atoms; fatty acids and their amine salts; andcombinations thereof and wherein the shearing mixing occurs at a shearrate in the range of less than or equal to 50,000 s⁻¹; and E) optionallyammonium nitrate.
 24. The process of claim 23 wherein the water is inthe range of about 0.01% to about 1% by weight of the composition.
 25. Aprocess for making a water in oil composition comprising shearing; A) afuel in the range of about 50% to about 99% by weight of thecomposition; B) a water in the range of less than about 1% by weight ofthe composition; C) a high molecular weight emulsifier in the range ofabout 1% to about 50% by weight of the composition; and D) a lowmolecular weight surfactants in the range of about 0.001% to about 15%by weight of the composition wherein the surfactant comprises naturalfats, non ionic surfactants, co-surfactant having about 1 to 24 carbonatoms; fatty acids and their amine salts; and combinations thereof andwherein the shearing mixing occurs at a shear rate in the range of lessthan or equal to 50,000 s⁻¹.
 26. The process of claim 25 wherein thewater is in the range of about 0.01% to about 1% by weight of thecomposition.